Method for producing scent intensifying washing and cleaning detergents

ABSTRACT

Scent intensifying washing and cleaning detergents or components for these detergents are manufactured in which a solid and essentially water-free premix is produced, said premis being comprised of washing and cleaning detergent compounds and/or washing and cleaning detergent materials. The premix contains at least 0.1 wt. % perfume referring to the premix and is subjected to granulation or compacted agglomeration. By virtue of the water-free method, subsequent drying steps do not apply in which the prefume is entirely or partially vaporized. The homogenous incorporation of the prefume leads to a substantially increased fragrance of both the product as well as the articles which are dampened or dried, especially textiles.

FIELD OF THE INVENTION

This invention relates to a process for the production of solidperfume-enhanced detergents. More particulaly, the invention relates toa process for the production of perfume-enhanced detergents with bulkdensities above 600 g/l by press agglomeration of a substantiallywater-free premix.

BACKGROUND OF THE INVENTION

The perfuming of solid detergents is now standard practice in the art.These products are perfumed on the one hand to provide the consumer witha recognizable and “unmistakable” product in conjunction with thestructure and color impression; on the other hand, the incorporation ofperfumes is intended to ensure that the articles treated with thedetergents, more particularly fabrics, are given a long-lasting perfumewhich is regarded by the consumer as a performance feature of theparticular detergent. Normally, those auxiliaries which do not make adirect contribution to the washing or cleaning process are added last tothe detergents. This procedure applies in particular to the “aesthetic”components, such as dyes and perfumes. Perfume is mostly incorporated byspraying the solid detergent granules with perfume which is optionallyfixed with powder components to the surface of the solid detergent. Thedisadvantage of this procedure is that the perfumes are not uniformlydistributed throughout the detergent and, in addition, can be partlyremoved during subsequently drying steps. In addition, the perfumeimpression of the detergents or rather the articles treated with them isoften not sufficiently intensive with this method of perfuming and canonly be made satisfactory by increasing the amount of perfume used.

The production of detergent granules is widely described in the priorart literature where, besides numerous patent specifications, there arean enormous number of publications concerned with this subject rangingfrom individual articles in specialist journals to complete works.

Compacted detergents and processes for their production are described,for example, in DE-A-39 26 253 and DE-A-195 19 139 (both Henkel KGaA).These two documents describe the extrusion of water-containing solidmixtures in the presence of added plasticizers and/or lubricants. Thereis no reference in either document to the use of perfumes. However,since the extrudates produced without perfumes contain water and have tobe subsequently dried, any perfuming required can only be carried out bythe conventional method of spraying onto the already dried extrudates.

Earlier German patent application 196 38 599.7 (Henkel KGaA) describes awater-free or substantially water-free extrusion process in whichsubsequent drying steps can be omitted because a substantiallywater-free premix with a water content of preferably no more than 15% byweight (this water not being present in free form) is extruded. Theperfuming of the extrudates obtained is not mentioned in this documenteither.

In order to solve the problem of the inadequate perfuming of articlestreated with detergents, perfume-containing particles, in which theperfume is so to speak “encapsulated”, have been described in the priorart. In particular, complexes of cyclodextrins and perfume are describedin the prior art as strong perfumes and fragrances for use indetergents, cf. for example EP 602 139, U.S. Pat. No. 5,236,615 and EP397 245 (all Procter & Gamble). Microencapsulated perfume oils are alsoused for this purpose, the perfume preferably being activated in adryer, cf. EP 376 385 (Procter & Gamble).

The solutions proposed in the cited prior art mainly extend to theperfuming of the treated and dried textiles. If it is desired that theproduct itself or the freshly washed and still damp laundry should alsobe olfactorily more noticeable, it has to be additionally sprayed withperfume in the conventional way which, besides the production of theperfume particles, involves another process step.

BRIEF DESCRIPTION OF THE INVENTION

Now, the problem addressed by the present invention was to provide aprocess by which it would be possible to produce perfume-enhanceddetergents or detergent components which would provide not only drylaundry, but also damp laundry with a stronger perfume and which, asdetergents per se, would also perfume much more noticeably thanconventionally perfumed detergents.

It has now been found that detergents having the required properties canbe obtained by producing a solid perfume-containing premix which issubstantially free from water and subjecting this premix to pressagglomeration.

The present invention relates to a process for the production ofperfume-enhanced detergents or detergent components with bulk densitiesabove 600 g/l, characterized in that a solid and substantiallywater-free premix containing at least 0.1% by weight of perfume, basedon the premix, is prepared from detergent compounds and/raw materialsand is subjected to press agglomeration.

DETAILED DESCRIPTION OF THE INVENTION

In the context of the invention, the expression “substantiallywater-free” is understood to apply to a state in which the content ofliquid water, i.e. water which is not present as water of hydrationand/or water of constitution, is below 2% by weight, preferably below 1%by weight and, more preferably, even below 0.5% by weight, based on thepremix. Accordingly, water can only be introduced into the process forproducing the premix in chemically and/or physically bound form or as aconstituent of the raw materials or compounds present as solids, but notas a liquid, solution or dispersion. The premix advantageously has atotal water content of not more than 15% by weight, i.e. the water ispresent in chemically and/or physically bound form and not in liquid,free form. In a particularly preferred embodiment, the content of waternot bound to zeolite and/or to silicates in the solid premix is no morethan 10% by weight and preferably no more than 7% by weight.

Detergents in the context of the invention are understood to becompositions which may be used for washing or cleaning without otheringredients normally having to be added. By contrast, a component fordetergents consists of at least 2 constituents normally used indetergents. However, components or so-called compounds are normally onlyused in admixture with other components, preferably together with othercompounds.

The ingredients used in the process according to the invention, exceptfor the nonionic surfactants liquid at temperatures below 45° C./1 barpressure, may be separately produced compounds and also raw materialswhich are present in powder or particulate form (fine to coarseparticles). The particles may be, for example, beads produced by spraydrying or (fluidized-bed) granules, etc. Basically, the composition ofthe compounds is not crucial to the invention, except for their watercontent which has to be gauged in such a way that the premix issubstantially water-free as defined above and preferably contains nomore than 10% by weight of water of hydration and/or water ofconstitution. In one preferred embodiment, overdried compounds are usedin the premix. Such compounds may be obtained, for example, by spraydrying, the temperature being controlled in such a way that the towerexit temperatures are above 70° C., for example 85° C. or higher. Solidcompounds serving as carriers for liquids, for example liquid nonionicsurfactants or silicone oil and/or paraffins, may also be used in thepremix. These compounds may contain water within the limits mentionedabove, the compounds being free-flowing and remaining free-flowing or atleast transportable even at relatively high temperatures of at least 45°C. In a particularly preferred embodiment, however, compounds containingat most 10% by weight and, more particularly, at most 7% by weight ofwater, based on the premix, are used in the premix. Free water, i.e.water which is not bound in any way to a solid and which is thereforepresent “in liquid form” is preferably not present at all in the premixbecause even very small quantities, for example of 0.2 or 0.5% byweight, based on the premix, are sufficient to partly dissolve thebasically water-soluble binder. This would result in the melting pointor softening point being reduced and the end product losing bothflowability and bulk density.

It has surprisingly been found that the solid raw material to which orthe solid compound in which the water is bound is by no meansirrelevant. Thus, water attached to builders, such as zeolite orsilicates (for a description of the substances, see below), moreparticularly to zeolite A, zeolite P or MAP and/or to zeolite X, may beregarded as relatively non-critical. By contrast, water bound to othersolid components than the builders mentioned is preferably present inthe premix in quantities of less than 3% by weight. In one particularlyadvantageous embodiment, the premix does not contain any water which isnot bound to the builders. However, this is technically difficult toachieve because, in general, traces of water at least are alwaysintroduced by the raw materials and compounds.

According to the invention, the substantially water-free premixescontain perfume, at least 0.1% by weight of perfume, based on thepremix, being added.

The incorporation of the perfume in the premix and the subsequent pressagglomeration step provides for the uniform distribution of the perfumesthroughout the detergent or the detergent component. Since asubstantially water-free premix is used, there is no need for subsequentdrying steps where perfume could partly or completely evaporate. Theselective incorporation of the perfume in the detergents or detergentcomponents also provides for a distinctly reduced loss of perfume intransit and during storage. Compared with conventionally perfumeddetergents, not only is the perfume much more uniformly distributed, theproduct also has a more intensive perfume impression. In this way,products can be perfumed with less perfume for the same olfactoryimpression or, alternatively, considerably improved perfume impressionscan be obtained for the same amount of perfume. The improvement in theperfume impression comes clearly to light not only on the perfumedproduct, but also on the treated articles, preferably textiles. Both ondamp and on dry laundry, the detergents leave behind a stronger perfumeimpression than conventionally perfumed press agglomerates. By virtue ofthe fact that the perfumes are uniformly distributed throughout thepress agglomerate as a whole, the problems associated with conventionalperfuming are also avoided. Since the capacity of the agglomerates toabsorb sprayed-on perfume is minimal and continues to decrease withincreasing degree of compression, most of the perfume adheres to thepowdering agent. The conventionally perfumed product inevitably movedaround in transit loses part of the powdering agent—which carries mostof the perfume—through friction. In the event of further movement, theseloose “fines” fall through the relatively coarse-particle bed of solidsand collect at the bottom of the containers, so that a certainpercentage of perfume makes virtually no contribution towards perfumingof the product and no contribution whatever to perfuming of the treatedarticles. These disadvantages are also avoided by the process accordingto the invention.

The perfume oils or perfumes used in the process according to the may beindividual perfume compounds, for example synthetic products of theester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Examplesof perfume compounds of the ester type are benzyl acetate, phenoxyethylisobutyrate, p-tert.butyl cyclohexyl acetate, linalyl acetate, dimethylbenzyl carbinyl acetate (DMBCA), phenyl ethyl acetate, benzyl acetate,ethyl methyl phenyl glycinate, allyl cyclohexyl propionate, styrallylpropionate, benzyl salicylate, cyclohexyl salicylate, floramate,melusate and jasmecyclate. The ethers include, for example, benzyl ethylether and Ambroxan; the aldehydes include, for example, linear alkanalscontaining 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, lilial and bourgeonal; the ketonesinclude, for example, ionones, α-isomethyl ionone and methyl cedrylketone; the alcohols include anethol, citronellol, eugenol, geraniol,linalool, phenyl ethyl alcohol and terpineol while the hydrocarbonsinclude, above all, terpenes, such as limonene and pinene. However,mixtures of different perfumes which together produce an attractiveperfume note are preferably used.

Perfume oils such as these may also contain natural perfume mixturesobtainable from vegetable sources, for example pine, citrus, jasmine,patchouli, rose or ylang-ylang oil. Also suitable are clary oil camomileoil, clove oil, melissa oil, mint oil, cinnamon leaf oil, lime blossomoil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil andlabdanum oil and orange blossom oil, neroli oil, orange peel oil andsandalwood oil.

The substantially water-free premix which is subjected to pressagglomeration preferably contains no dust-fine particles and, inparticular, no particles below 200 μm in size. Particularly preferredparticle size distributions are those where at least 90% by weight ofthe particles are at least 400 μm in diameter. In one particularlypreferred embodiment of the invention, at least 70% by weight,preferably at least 80% by weight and more preferably up to 100% byweight of the detergents or detergent components produced by pressagglomeration consist of spherical or substantially spherical(bead-like) particles with a particle size distribution where at least60% by weight of the particles are between 0.8 and 2.0 mm in size.

The solid and substantially water-free premix contains typical soliddetergent ingredients such as, for example, builders, solid surfactants,bleaching agents, bleach activators, polymers and other typicalingredients. As described above, these ingredients may be usedindividually or in the form of compounds optionally impregnated withliquid or paste-form detergent ingredients such as, for example,silicone oils, paraffins or liquid nonionic surfactants. Premixescontaining individual raw materials and/or compounds which are presentas solids at room temperature/1 bar pressure and which have a melting orsoftening point of no lower than 45° C. and optionally up to 20% byweight, preferably up to 15% by weight and more preferably up to 10% byweight, based on the premix, of nonionic surfactants liquid attemperatures below 45° C./1 bar pressure are preferably used inaccordance with the present invention. The nonionic surfactants used arepreferably the alkoxylated alcohols typically used in detergents, suchas fatty or oxo alcohols, so that a preferred process is characterizedin that, in addition to the solid constituents, the premix additionallycontains up to 20% by weight, preferably up to 15% by weight and morepreferably up to 10% by weight of nonionic surfactants liquid attemperatures below 45° C./1 bar pressure, more particularly thealkoxylated alcohols typically used in detergents, such as fattyalcohols or oxo alcohols containing between 8 and 20 carbon atoms and,in particular, an average of 3 to 7 ethylene oxide units per mole ofalcohol, the liquid nonionic surfactants preferably being added inadmixture with the perfume.

In order to facilitate the press agglomeration of the premix and toimprove the physical properties of the perfume-enhanced detergents ordetergent components obtained by press agglomeration, the premix maycontain a raw material or a compound which acts as a binder anddisintegration aid. These binders and disintegration aids act aslubricants and adhesives in the press agglomeration step, bonding thesolid particles of the premix to one another and making it easier forthe premix to pass through the compression zone of the pressagglomeration units. In addition, as water-soluble binders, theyfacilitate the redissolution of the press agglomerates because they actas disintegrators in water. In a preferred process according to theinvention, the premix contains at least one raw material or one compoundwhich is present in solid form at temperatures below 45° C./1 barpressure, but which exists as a melt during the press agglomerationstep, this melt acting as a polyfunctional water-soluble binder which,in the production of the detergents, acts both as a lubricant and as anadhesive for the solid detergent compounds or raw materials, but has adisintegrating effect during the redissolution of the detergent inwater.

Binders suitable for use in the process according to the invention aresolid at temperatures below 45° C./1 bar pressure, but exist as a meltunder the process conditions of the press agglomeration step. The bindermay be incorporated in the premix by spraying a melt of the binder orbinder mixture onto the premix or by adding such a melt dropwise to thepremix. However, the binder (mixture) may also be incorporated in thepremix as a fine-particle solid.

The nature of a suitable binder and the temperature prevailing in thecompacting step of the press agglomeration process are interdependent.Since it has been found to be of advantage for the binder to bedistributed as uniformly as possible in the material to be compacted inthe compacting step of the process, temperatures at which the binder atleast softens and, preferably, is present completely and not just partlyin molten form must prevail in the compacting step of the process. If,therefore, the binder selected has a high melting point or a highsoftening point, a temperature which ensures that the binder melts mustbe established in the compacting step of the process. In addition,depending on the desired composition of the end product,temperature-sensitive raw materials should also lend themselves toprocessing. In this case, the upper temperature limit is imposed by thedecomposition temperature of the sensitive raw material, the compactingstep preferably being carried out at temperatures significantly belowthe decomposition temperature of this raw material. By contrast, thelower limit to the melting point or rather to the softening point is ofsuch considerable significance because, with softening points or meltingpoints below 45° C., the end product obtained will generally tend tobecome tacky even at room temperature and slightly elevated temperaturesof around 30° C., i.e. at summer temperatures, and under storage ortransportation conditions. It has proved to be of particular advantageto carry out the compacting step a few degrees, for example 2 to 20° C.,above the melting point or rather above the softening point.

Without wishing to be confined to this theory, applicants are of theview that, by virtue of the homogeneous distribution of the binder inthe premix, the solid compounds and the individual raw materialsoptionally present are coated by the binder under the process conditionsof the compacting step and then bonded to one another in such a way thatthe end products are made up almost exactly of these numerous smallindividual particles that are held together by the binder which acts asa preferably thin partition between these individual particles. Inidealized form, the structure may be described as resembling a honeycombin which the cells are filled with solids (compounds or individual rawmaterials). On contact with water, even cold water, i.e. for example atthe beginning of an automatic wash cycle, the thin partitions mentioneddissolve or disintegrate almost instantaneously. Surprisingly, this isalso the case when, basically, the binder does not dissolve quickly inwater at room temperature, for example because of a crystal structure.However, binders which, in a test as described above, can be almostcompletely dissolved in 90 seconds in a concentration of 8 g of binderto 1 liter of water at 30° C. are preferably used.

Accordingly, the binder(s) must be of the type which retain(s) its/theiradhesive properties, even at temperatures well above the melting pointor rather the softening point. On the other hand, it is also crucial tothe choice of the binder(s) used in terms of type and quantity that,although the binding properties remain intact after recooling within theend product, so that the cohesion of the end product is ensured, the endproduct itself does not become tacky under standard storage andtransportation conditions.

In the interests of simplicity, the binder will hereinafter be referredto solely as “a binder” or “the binder”. However, it is emphasized that,basically, several different binders and mixtures of different bindersmay always be used.

One preferred embodiment of the invention is characterized by the use ofa binder which is completely present as a melt at temperatures of up toat most 130° C., preferably at temperatures of up to at most 100° C. andmore preferably at temperatures of up to 90° C. Accordingly, the bindershould be selected according to the particular process and processconditions or, if it is desired to use a certain binder, the processconditions, particularly the process temperature, should be adapted tothe binder.

Preferred binders which may be used either individually or in the formof mixtures with other binders are polyethylene glycols,1,2-polypropylene glycols and modified polyethylene glycols andpolypropylene glycols. The modified polyalkylene glycols include, inparticular, the sulfates and/or the disulfates of polyethylene glycolsor polypropylene glycols with a relative molecular weight of 600 to12,000 and, more particularly, in the range from 1,000 to 4,000. Anothergroup consists of mono- and/or disuccinates of polyalkylene glycolswhich, in turn, have relative molecular weights of 600 to 6,000 and,preferably, in the range from 1,000 to 4,000. A more detaileddescription of the modified polyalkylene glycol ethers can be found inthe disclosure of International patent application WO-A-93/02176. In thecontext of the invention, polyethylene glycols include polymers whichhave been produced using C₃₋₅ glycols and also glycerol and mixturesthereof besides ethylene glycol as starting molecules. In addition, theyalso include ethoxylated derivatives, such as trimethylol propanecontaining 5 to 30 EO.

The polyethylene glycols preferably used may have a linear or branchedstructure, linear polyethylene glycols being particularly preferred.

Particularly preferred polyethylene glycols include those havingrelative molecular weights in the range from 2,000 to 12,000 and,advantageously, around 4,000. Polyethylene glycols with relativemolecular weights below 3,500 and above 5,000 in particular may be usedin combination with polyethylene glycols having a relative molecularweight of around 4,000. More than 50% by weight, based on the totalquantity of polyethylene glycols, of such combinations mayadvantageously contain polyethylene glycols with a relative molecularweight of 3,500 to 5,000. However, polyethylene glycols which,basically, are present as liquids at room temperature/1 bar pressure,above all polyethylene glycol with a relative molecular weight of 200,400 and 600, may also be used as binders. However, these basicallyliquid polyethylene glycols should only be used in the form of a mixturewith at least one other binder, this mixture again having to satisfy therequirements according to the invention, i.e. must have a melting pointor softening point at least above 45° C.

The modified polyethylene glycols also include polyethylene glycolsend-capped on one or more sides, the end groups preferably being C₁₋₁₂alkyl chains which may be linear or branched. In particular, theterminal groups have C₁₋₆ and, above all, C₁₋₄ alkyl chains, isopropyland isobutyl or tert.butyl being other possible alternatives.

Polyethylene glycol derivatives end-capped on one side may alsocorrespond to the formula C_(x)(EO)_(y)(PO)_(z), where C_(x) may be aC₁₋₂₀ alkyl chain, y may be a number of 50 to 500 and z may be a numberof 0 to 20. Where z=0, the polyethylene glycol derivatives overlap withcompounds corresponding to the preceding paragraph. However, EO-POpolymers (x=0) may also serve as binders.

Other suitable binders which may be used in water-free or substantiallywater-free press agglomeration processes are disclosed in earlier Germanpatent application 196 38 599.7 and may also be used in accordance withthe present invention.

According to the teaching of earlier German patent application 196 38599.7, the content of binder(s) in the premix is preferably at least 2%by weight, but less than 15% by weight, preferably less than 10% byweight and more preferably from 3 to 6% by weight, based on the premix.The polymers swollen in the absence of water in particular are used inquantities below 10% by weight, advantageously in quantities of 4 to 8%by weight and preferably in quantities of 5 to 6% by weight. Accordingto the invention, the minimum binder content of the premix may befurther reduced by virtue of the use of perfume therein (see below).

In one preferred embodiment of the process according to the invention,the solids for producing the solid free-flowing premix are first mixedtogether in a standard mixer and/or granulator at room temperature toslightly elevated temperatures, which are preferably below the meltingtemperature or the softening point of the binder, more particularly attemperatures of up to 35° C.

The binders are preferably added as the last component. As mentionedabove, they may be added as solids, i.e. at a processing temperaturebelow their melting point or rather their softening point, or as a melt.However, they are advantageously added under such conditions that thebinder is uniformly distributed in the mixture of solids. With veryfine-particle binders, this can be done at temperatures below 40° C.,for example at temperatures of the binder of 15 to 30° C. However, thebinder preferably has temperatures at which it is already present in theform of a melt, i.e. above the softening point, more particularly in theform of a complete melt. Preferred melt temperatures are in the rangefrom 60 to 150° C., melt temperatures in the range from 80 to 120° C.being particularly preferred. During the mixing process, which takesplace at room temperature to slightly elevated temperature, but belowthe softening point or rather the melting point of the binder, the meltsolidifies almost instantaneously and, according to the invention, thepremix is present in solid free-flowing form. At all events, the mixingprocess is advantageously continued until the melt has solidified andthe premix is present in solid, free-flowing form.

Through the incorporation of the perfume in the premix, the percentagecontent of binder(s) can be reduced. Since the perfumes act aslubricants and, by virtue of their uniform distribution throughout thepress agglomerate, do not impede the redissolution process despite theirgenerally hydrophobic character, it is possible further to reduce thebinder content of the premix mentioned in earlier German patentapplication 196 38 599.7 (more than 2 to less than 15% by weight,preferably less than 10% by weight and more preferably 3 to 6% byweight), so that binder contents of 1 to 5% by weight and preferably 2to 4% by weight may be used. Preferred processes are characterized bythe use of a premix of which the binder content is at least 1% byweight, but less than 10% by weight, preferably less than 8% by weightand more preferably from 2 to 4% by weight, based on the premix. As thebinder content decreases, larger quantities of nonionic surfactant canbe incorporated so that it is possible by the process according to theinvention to produce perfume-enhanced high-surfactant press agglomerateswhich could not be produced by existing methods. In this case, thepremix preferably contains distinctly more than the minimum quantity of0.1% by weight of perfume. Preferred processes according to theinvention are characterized in that the premix contains more than 0.15%by weight, preferably more than 0.2% by weight and more preferably morethan 0.3% by weight of perfume.

The perfume may be incorporated in the premix at virtually any stage ofits production. For example, the solids may be completely or partlyintroduced into a standard mixer and/or granulator at room temperature,as described above, and the perfume may be added to or sprayed onto themoving bed of solids. However, the perfume may also be added to thesolids together with the binder, as described above. In this case,perfume may be mixed with solid binder or the perfume may beincorporated in a separately prepared melt of the binder and thepaste-like or liquid binder/perfume mixture may be added to the solids.Any of the methods of incorporation mentioned above may of course alsobe combined with one another, part of the perfume always beingintroduced into the premix in different ways. If nonionic surfactantsare used in the process according to the invention, the perfume ispreferably added in the form of a mixture with the nonionic surfactants,in which case mixtures of binder, nonionic surfactant and perfume mayalso be prepared and used.

The fact that the process is carried out in the substantial absence ofwater enables the perfume to be incorporated in the premix because thereis no need for subsequent drying steps where perfume losses could occur.In addition, the fact that the process is carried out under theseconditions has the advantage that peroxy bleaching agents can beprocessed without any losses of activity, in addition to which peroxybleaching agents and bleach activators (for an exact description, seebelow) can be processed together without any danger of serious losses ofactivity.

The compacting of the pile of particles (premix) on the one hand reducesporosity in the press agglomeration process while, on the other hand,particle adhesion is strenghtened by the plastic deformation of thecontact zones so that materials which largely lend themselves to plasticdeformation give compactates of high strength while elasticallydeformable particles with brittle behavior are more difficult tocompress. Compression behavior can be improved by the addition ofbinders. The press agglomeration process to which the solid andsubstantially water-free premix is subjected may be carried out invarious agglomerators. Press agglomeration processes are classifiedaccording to the type of agglomerator used. The four most common pressagglomeration processes—which are preferred to the purposes of theinvention—are extrusion, roll compacting, pelleting and tabletting, sothat preferred agglomeration processes for the purposes of the presentinvention are extrusion, roll compacting, pelleting and tablettingprocesses.

One feature common to all these processes is that the premix iscompacted and plasticized under pressure and the individual particlesare pressed against one another with a reduction in porosity and adhereto one another. In all the processes (but with certain limitations inthe case of tabletting), the tools may be heated to relatively hightemperatures or may be cooled to dissipate the heat generated by shearforces. The actual compacting process is preferably carried out atprocessing temperatures which, at least in the compacting step, at leastcorrespond to the temperature of the softening point if not to thetemperature of the melting point of the binder. In one preferredembodiment of the invention, the process temperature is significantlyabove the melting point or above the temperature at which the binder ispresent as a melt. In a particularly preferred embodiment, however, theprocess temperature in the compacting step is no more than 20° C. abovethe melting temperature or the upper limit to the melting range of thebinder. Although, technically, it is quite possible to adjust evenhigher temperatures, it has been found that a temperature difference inrelation to the melting temperature or to the softening temperature ofthe binder of 20° C. is generally quite sufficient and even highertemperatures do not afford additional advantages. Accordingly it isparticularly preferred, above all on energy grounds, to carry out thecompacting step above, but as close as possible to, the melting point orrather to the upper temperature limit of the melting range of thebinder. Controlling the temperature in this way has the furtheradvantage that even heat-sensitive raw materials, for example peroxybleaching agents, such as perborate and/or percarbonate, and alsoenzymes, can be processed increasingly without serious losses of activesubstance. The possibility of carefully controlling the temperature ofthe binder, particularly in the crucial compacting step, i.e. betweenmixing/homogenizing of the premix and shaping, enables the process to becarried out very favorably in terms of energy consumption and with nodamaging effects on the heat-sensitive constituents of the premixbecause the premix is only briefly exposed to the relatively hightemperatures. In preferred press agglomeration processes, the workingtools of the press agglomerator (the screw(s) of the extruder, theroller(s) of the roll compactor and the pressure roller(s) the pelletpress) have a temperature of at most 150° C., preferably of at most 100°C. and, in a particularly preferred embodiment, at most 75° C., theprocess temperature being 30° C. and, in a particularly preferredembodiment, at most 20° C. above the melting temperature or rather theupper temperature limit to the melting range of the binder. The heatexposure time in the compression zone of the press agglomerators ispreferably at most 2 minutes and, more preferably, between 30 secondsand 1 minute.

The temperature of the compacted material immediately after leaving theproduction unit is preferably not more than 90° C. and, in oneparticularly preferred embodiment, is between 35 and 85° C. It has beenfound that exit temperatures, above all in the extrusion process, of 40to 80° C., for example up to 70° C., are particularly advantageous.

In one preferred embodiment of the invention, the process according tothe invention is carried out by extrusion as described, for example inEuropean patent EP-B-0 486 592 (Henkel KGBA) or International patentapplications WO-A-93/02176 (Henkel KGaA) and WO-A-94/09111 (HenkelKGaA). In this extrusion process, a solid premix is extruded underpressure to form a strand and, after emerging from the multiple-boreextrusion die, the strands are cut into granules of predetermined sizeby means of a cutting unit. The solid, homogeneous premix contains aplasticizer and/or lubricant of which the effect is to soften the premixunder the pressure applied or under the effect of specific energy, sothat it can be extruded. Preferred plasticizers and/or lubricants aresurfactants and/or polymers which, except for the nonionic surfactantsmentioned above, are introduced into the premix in solid form, but notin liquid form and especially not in the form of an aqueous liquid inaccordance with the present invention.

Particulars of the actual extrusion process can be found in theabove-cited patents and patent applications to which reference is herebyexpressly made. In one preferred embodiment of the invention, the premixis delivered, preferably continuously, to a planetary roll extruder orto a twin-screw extruder with co-rotating or contra-rotating screws, ofwhich the barrel and the extrusion/granulation head can be heated to thepredetermined extrusion temperature. Under the shear effect of theextruder screws, the premix is compacted under a pressure of preferablyat least 25 bar or—with extremely high throughputs—even lower, dependingon the apparatus used, plasticized, extruded in the form of fine strandsthrough the multiple-bore extrusion die in the extruder head and,finally, size-reduced by means of a rotating cutting blade, preferablyinto spherical or cylindrical granules. The bore diameter of themultiple-bore extrusion die and the length to which the strands are cutare adapted to the selected granule size. In this embodiment, granulesare produced in a substantially uniformly predeterminable particle size,the absolute particle sizes being adaptable to the particularapplication envisaged. In general, particle diameters of up to at most0.8 cm are preferred. Important embodiments provide for the productionof uniform granules in the millimeter range, for example in the rangefrom 0.5 to 5 mm and more particularly in the range from about 0.8 to 3mm. In one important embodiment, the length-to-diameter ratio of theprimary granules is in the range from about 1:1 to about 3:1. In anotherpreferred embodiment, the still plastic primary granules are subjectedto another shaping process step in which edges present on the crudeextrudate are rounded off so that, ultimately, spherical orsubstantially spherical extrudate granules can be obtained. If desired,small quantities of drying powder, for example zeolite powder, such aszeolite NaA powder, may be used in this step. This shaping step may becarried out in commercially available spheronizers. It is important inthis regard to ensure that only small quantities of fines are formed inthis stage. According to the present invention, however, there is noneed for drying, which is described as a preferred embodiment in theprior art documents cited above, because the process according to theinvention is carried out in the substantial absence of water, i.e.without the addition of free non-bound water.

Alternatively, extrusion/compression steps may also be carried out inlow-pressure extruders, in a Kahl press (Amandus Kahl) or in a so-calledBextruder.

In one particularly preferred embodiment of the invention, thetemperature prevailing in the transition section of the screw, thepre-distributor and the extrusion die is controlled in such a way thatthe melting temperature of the binder or rather the upper limit to themelting range of the binder is at least reached and preferably exceeded.The temperature exposure time in the compression section of the extruderis preferably less than 2 minutes and, more particularly, between 30seconds and 1 minute.

The brief residence times together with the absence of water enableperoxy bleaching agents, optionally in conjunction with bleachactivators, to be extruded even at relatively high temperatures withoutsuffering serious losses of activity.

In one particularly advantageous embodiment of the invention, the binderused has a melting temperature or a melting range of up to 75° C. Inthis embodiment, process temperatures at most 10° C. and, moreparticularly, at most 5° C. above the melting temperature or rather theupper temperature limit of the melting range of the binder have provedto be particularly favorable.

Under these process conditions, the binder—in addition to its functionsas mentioned hitherto—also acts as a lubricant and prevents or at leastreduces the formation of sticky deposits on machine walls and compactingtools. This applies not only to extrusion but equally, for example, toprocessing in continuous mixers/granulators or rolls.

As in the extrusion process, it is also preferred in the otherproduction processes to subject the primary granules/compactates formedto another shaping process step, more particularly spheronizing, sothat, ultimately, spherical or substantially spherical (bead-like)granules can be obtained. A key feature of another preferred embodimentof the invention is that the particle size distribution of the premix isconsiderably broader than that of the end product according to theinvention/produced in accordance with the invention. The premix may havemuch larger fine-particle components, even dust-fine components and mayoptionally contain larger numbers of relatively coarse particles,although a premix with a relatively broad particle size distribution andwith relatively high percentages of fine particles is preferablyconverted into an end product with a relatively narrow particle sizedistribution and relatively small numbers of fines.

By virtue of the fact that the process according to the invention iscarried out in the substantial absence of water, i.e. except for thewater present as “impurity” in the solid raw materials used, not only isthe danger of gelation of the surface-active raw materials in theproduction process itself minimized or ruled out altogether, anecologically valuable process is also provided because elimination ofthe need for a subsequent drying step not only saves energy, emissionswhich occur predominantly in conventional drying techniques can also beavoided. In addition, the absence of subsequent drying steps enables theperfumes to be incorporated in the premix and thus provides for theproduction of perfume-enhanced detergents or detergent components.

In another preferred embodiment of the present invention, the processaccording to the invention is carried out by roll compacting. In thisvariant, the perfume-containing, solid and substantially water-freepremix is introduced between two rollers—either smooth or provided withdepressions of defined shape—and rolled under pressure between the tworollers to form a sheet-like compactate. The rollers exert a high linearpressure on the premix and may be additionally heated or cooled asrequired. Where smooth rollers are used, smooth untextured compactatesheets are obtained. By contrast, where textured rollers are used,correspondingly textured compactates, in which for example certainshapes can be imposed in advance on the subsequent detergent particles,can be produced. The sheet-like compactate is then broken up intosmaller pieces by a chopping and size-reducing process and can thus beprocessed to granules which can be further refined and, moreparticularly, converted into a substantially spherical shape by furthersurface treatment processes known per se.

In roll compacting, too, the temperature of the pressing tools, i.e. therollers, is preferably at most 150° C., more preferably at most 100° C.and most preferably at most 75° C. Particularly preferred productionprocesses based on roll compacting are carried out at temperatures 10°C. and, in particular, at most 5° C. above the melting temperature ofthe binder or the upper temperature limit of the melting range of thebinder. The temperature exposure time in the compression section of therollers—either smooth or provided with depressions of defined shape—ispreferably at most 2 minutes and, more particularly, between 30 secondsand 1 minute.

In another preferred embodiment of the present invention, the processaccording to the invention is carried out by pelleting. In this process,the perfume-containing, solid and substantially water-free premix isapplied to a perforated surface and is forced through the perforationsand at the same time plasticized by a pressure roller. In conventionalpellet presses, the premix is compacted under pressure, plasticized,forced through a perforated surface in the form of fine strands by meansof a rotating roller and, finally, is size-reduced to granules by acutting unit. The pressure roller and the perforated die may assume manydifferent forms. For example, flat perforated plates are used, as areconcave or convex ring dies through which the material is pressed by oneor more pressure rollers. In perforated-plate presses, the pressurerollers may also be conical in shape. In ring die presses, the dies andpressure rollers may rotate in the same direction or in oppositedirections. A press suitable for carrying out the process according tothe invention is described, for example, in DE-OS 38 16 842 (SchlüterGmbH). The ring die press disclosed in this document consists of arotating ring die permeated by pressure bores and at least one pressureroller operatively connected to the inner surface thereof which pressesthe material delivered to the die space through the pressure bores intoa discharge unit. The ring die and pressure roller are designed to bedriven in the same direction which reduces the shear load applied to thepremix and hence the increase in temperature which it undergoes.However, the pelleting process may of course also be carried out withheatable or coolable rollers to enable the premix to be adjusted to arequired temperature.

In pelleting, too, the temperature of the pressing tools, i.e. thepressure rollers, is preferably at most 150° C., more preferably at most100° C. and most preferably at most 75° C. Particularly preferredproduction processes based on pelleting are carried out at temperatures10° C. and, in particular, at most 5° C. above the melting temperatureof the binder or the upper temperature limit of the melting range of thebinder.

Another press agglomeration process which may be used in accordance withthe invention is tabletting. In view of the size of the tabletsproduced, it may be appropriate in the tabletting variant to addconventional disintegration aids, for example cellulose and cellulosederivatives, more particularly in a coarse form, or crosslinked PVP, inaddition to the binder described above to facilitate the disintegrationof the tablets in the wash liquor.

In one preferred embodiment, the invention provides a perfume-enhanced,extruded, roll-compacted or pelleted detergent of which at least 80% byweight consists of compounds produced in accordance with the inventionand/or treated raw materials. More particularly, at least 80% by weightof an extruded, roll-compacted or pelleted detergent consists of a basicagglomerate produced in accordance with the invention. The remainingconstituents may have been produced and incorporated by any knownprocess. Preferably, however, these remaining constituents also—whichmay be compounds and/or treated raw materials—will have been produced bythe process according to the invention. Above all, this enables thebasic granules and remaining constituents to be produced withsubstantially the flow behavior, bulk density, size and particle sizedistribution.

The particulate press agglomerates obtained may either be directly usedas detergents or may be aftertreated and/or compounded beforehand byconventional methods. Conventional aftertreatments include, for example,powdering with fine-particle detergent ingredients which, in general,produces a further increase in bulk density. However, another preferredaftertreatment is the procedure according to German patent applicationsDE-A-195 24 287 and DE-A-195 47 457, according to which dust-like or atleast fine-particle ingredients (so-called fine components) are bondedto the particulate end products produced by the process according to theinvention which serve as core. This results in the formation ofdetergents which contain these so-called fine components as an outershell. Advantageously, this is again done by melt agglomeration usingthe same binders as in the process according to the invention. On thesubject of the melt agglomeration of fine components onto the basicgranules according to the invention and produced in accordance with theinvention, reference is specifically made to the disclosure of Germanpatent applications DE-A-195 24 287 and DE-A-195 47 457.

Both the perfume-enhanced detergents, of which at least 80% by weightconsist of press agglomerates produced in accordance with the invention,and the press agglomerates themselves may be additionally sprayed withperfume in a subsequent step. The conventional perfuming variant, i.e.powdering and spraying with perfume, can also be carried out with thepress agglomerates according to the invention.

Advantageously, at least 30% by weight, preferably at least 40% byweight and more preferably at least 50% by weight of the total perfumepresent in the perfume-enhanced detergents according to the inventionare introduced into the detergent by the production process according tothe invention, i.e. incorporated in the press agglomerates, while theremaining 70% by weight, preferably 60% by weight and more preferably50% by weight of the total perfume present may be sprayed onto orotherwise applied to the press agglomerates which may optionally besurface-treated.

By dividing the total perfume content of the detergents into perfumepresent in the press agglomerates and perfume adhering to the pressagglomerates, it is possible to achieve a number of product featureswhich are only possible through the process according to the invention.For example, the total perfume content of the detergents can be dividedinto two portions x and y, portion x consisting of firmly adheringperfume oils, i.e. less volatile perfume oils, and portion y consistingof more volatile perfume oils.

Now, it is possible to produce detergents where the percentage ofperfume introduced into the detergent through the press agglomerates ismainly made up of firmly adhering perfumes. In this way, firmly adheringperfumes which are intended to perfume the treated articles, moreespecially textiles, are “retained” in the product and thus developtheir effect primarily on the treated laundry. By contrast, the morereadily volatile perfumes contribute towards more intensive perfuming ofthe detergents per se. In this way, it is also possible to producedetergents which, as detergents, have a perfume that differs from theperfume of the treated articles. There are virtually no limits in thisregard to the creativity of perfumists because almost limitlesspossibilities for perfuming the detergents and—through thedetergents—the articles treated with them exist on the one hand throughthe choice of the perfumes and on the other hand through the choice ofthe method used to incorporate them in the detergents.

The principle described above can of course also be reversed byincorporating the more readily volatile perfumes in the pressagglomerates and spraying the less volatile firmly adhering perfumesonto the detergents. In this way, the loss of the more readily volatileperfumes from the pack in storage and in transit is minimized while theperfume characteristic of the detergents is determined by the morefirmly adhering perfumes.

The general description of the perfumes suitable for use in accordancewith the invention (see above) represented the various classes ofperfumes in general terms. In order to be noticeable, a perfume has tobe volatile, its molecular weight being an important factor along withthe nature of the functional groups and the structure of the chemicalcompound. Thus, most perfumes have molecular weights of up to about 200dalton, molecular weights of 300 dalton and higher being more theexception. In view of the differences in volatility of perfumes, theodor of a perfume or fragrance composed of several perfumes changesduring the evaporation process, the odor impressions being divided intothe top note, the middle note or body and the end note or dry out. Sinceodor perception is also based to a large extent on odor intensity, thetop note of a perfume or fragrance does not consist solely of readilyvolatile compounds whereas the end note or dry out consists largely ofless volatile, i.e. firmly adhering, perfumes. In the composition ofperfumes, more readily volatile perfumes may be fixed, for example, tocertain “fixatives”, which prevents them from vaporizing too rapidly.The above-described embodiment of the present invention, in which themore readily volatile perfumes or fragrances are incorporated in thepress agglomerate, is one such method of fixing a perfume. Accordingly,in the following classification of perfumes into “readily volatile” and“firmly adhering” perfumes, nothing is said about the odor impression orabout whether the corresponding perfume is perceived as a top note ormiddle note.

Firmly adhering perfumes suitable for use in accordance with the presentinvention are, for example, the essential oils, such as angelica rootoil, aniseed oil, amica flowers oil, basil oil, bay oil, bergamot oil,champax blossom oil, silver fir oil, silver fir cone oil, elemi oil,eucalyptus oil, fennel oil, pine needle oil, galbanum oil, geranium oil,ginger grass oil, guaiac wood oil, Indian wood oil, helichrysum oil, hooil, ginger oil, iris oil, cajeput oil, sweet flag oil, camomile oil,camphor oil, canaga oil, cardamom oil, cassia oil, Scotch fir oil,copaiba balsam oil, coriander oil, spearmint oil, caraway oil, cuminoil, lavender oil, lemon grass oil, limette oil, mandarin oil, melissaoil, amber seed oil, myrrh oil, clove oil, neroli oil, niaouli oil,olibanum oil, orange oil, origanum oil, palmarosa oil, patchouli oil,Peru balsam oil, petit grain oil, pepper oil, peppermint oil, pimentooil, pine oil, rose oil, rosemary oil, sandalwood oil, celery seed oil,lavender spike oil, Japanese anise oil, turpentine oil, thuja oil, thymeoil, verbena oil, vetiver oil, juniper berry oil, wormwood oil,wintergreen oil, ylang-ylang oil, ysop oil, cinnamon oil, cinnamon leafoil, citronella oil, citrus oil and cypress oil.

However, relatively high-boiling or solid perfumes of natural orsynthetic origin may also be used in accordance with the invention asfirmly adhering perfumes or perfume mixtures. These compounds includethose mentioned in the following and mixtures thereof: ambrettolide,α-amyl cinnamaldehyde, anethole, anisaldehyde, anisalcohol, anisole,methyl anthranilate, acetophenone, benzyl acetone, benzaldehyde, ethylbenzoate, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzoate,benzyl formate, benzyl valerate, bomeol, bomyl acetate, α-bromostyrene,n-decyl aldehyde, n-dodecyl aldehyde, eugenol, eugenol methyl ether,eucalyptol, farnesol, fenchone, fenchyl acetate, geranyl acetate,geranyl formiate, heliotropin, methyl heptyne carboxylate, heptaldehyde,hydroquinone dimethyl ether, hydroxycinnamaldehyde, hydroxycinnamylalcohol, indole, irone, isoeugenol, isoeugenol methyl ether, isosafrol,jasmone, camphor, carvacrol, carvone, p-cresol methyl ether, coumarin,p-methoxyacetophenone, methyl-n-amyl ketone, methyl anthranilic acidmethyl ester, p-methyl acetophenone, methyl chavicol, p-methylquinoline, methyl-β-naphthyl ketone, methyl-n-nonyl acetaldehyde,methyl-n-nonyl ketone, muskone, β-naphthol ethyl ether, β-naphtholmethyl ether, nerol, nitrobenzene, n-nonyl aldehyde, nonyl alcohol,n-octyl aldehyde, p-oxyacetophenone, pentadecanolide, β-phenyl ethylalcohol, phenyl acetaldehyde dimethyl acetal, phenyl acetic acid,pulegone, safrol, isoamyl salicylate, methyl salicylate, hexylsalicylate, cyclohexyl salicylate, santalol, scatol, terpineol, thymene,thymol, γ-undecalactone, vanillin, veratrum aldehyde, cinnamaldehyde,cinnamyl alcohol, cinnamic acid, ethyl cinnamate, benzyl cinnamate.

The more readily volatile perfumes include, in particular, therelatively low-boiling perfumes of natural or synthetic origin which maybe used either individually or in the form of mixtures. Examples of morereadily volatile perfumes are alkyl isothiocyanates (alkyl mustardoils), butanedione, limonene, linalool, linalyl acetate and propionate,menthol, menthone, methyl-n-heptenone, phellandrene, phenylacetaldehyde, terpinyl acetate, citral, citronellal.

The possible other ingredients of the detergents according to theinvention and the components used in the process according to theinvention are described in detail in the following.

Important ingredients of the detergents according to the invention andingredients which are used in the process according to the invention aresurfactants, particularly anionic surfactants, which should be presentin the detergents according to the invention or in detergents producedin accordance with the invention in quantities of at least 0.5% byweight. Anionic surfactants include, in particular, sulfonates andsulfates and also soaps.

Preferred surfactants of the sulfonate type are preferably C₉₋₁₃ alkylbenzenesulfonates, olefin sulfonates, i.e. mixtures of alkene andhydroxy-alkane sulfonates, and the disulfonates obtained, for example,from C₁₂₋₁₈ monoolefins with an internal or terminal double bond bysulfonation with gaseous sulfur trioxide and subsequent alkaline oracidic hydrolysis of the sulfonation products.

Other suitable surfactants of the sulfonate type are the alkanesulfonates obtained from C₁₂₋₁₈ alkanes, for example bysulfochlorination or sulfoxidation and subsequent hydrolysis orneutralization.

The esters of α-sulfofatty acids (ester sulfonates), for example theα-sulfonated methyl esters of hydrogenated coconut oil, palm kernel oilor tallow fatty acids, which are obtained by α-sulfonation of the methylesters of fatty acids of vegetable and/or animal origin containing 8 to20 carbon atoms in the fatty acid molecule and subsequent neutralizationto water-soluble monosalts are also suitable. The esters in question arepreferably the α-sulfonated esters of hydrogenated coconut acid, palmoil acid, palm kernel oil acid or tallow acid, although sulfonationproducts of unsaturated fatty acids, for example oleic acid, may also bepresent in small quantities, preferably in quantities of not more thanabout 2 to 3% by weight. α-Sulfofatty acid alkyl esters with an alkylchain of not more than 4 carbon atoms in the ester group, for examplemethyl esters, ethyl esters, propyl esters and butyl esters, areparticularly preferred. The methyl esters of α-sulfofatty acids (MES)and saponified disalts thereof are used with particular advantage.

Other suitable anionic surfactants are sulfonated fatty acid glycerolesters, i.e. the monoesters, diesters and triesters and mixtures thereofwhich are obtained where production is carried out by esterification bya monoglycerol with 1 to 3 moles of fatty acid or in thetransesterification of triglycerides with 0.3 to 2 moles of glycerol.

Preferred alk(en)yl sulfates are the alkali metal salts and, inparticular, the sodium salts of the sulfuric acid semiesters of C₁₂₋₁₈fatty alcohols, for example coconut alcohol, tallow alcohol, lauryl,myristyl, cetyl or stearyl alcohol, or C₁₀₋₂₀ oxoalcohols and thecorresponding semiesters of secondary alcohols with the same chainlength. Other preferred alk(en)yl sulfates are those with the chainlength mentioned which contain a synthetic, linear alkyl chain based ona petrochemical and which are similar in their degradation behavior tothe corresponding compounds based on oleochemical raw materials. C₁₂₋₁₆alkyl sulfates and C₁₂₋₁₅ alkyl sulfates and also C₁₄₋₁₅ alkyl sulfatesare particularly preferred from the washing performance point of view.Other suitable anionic surfactants are 2,3-alkyl sulfates which may beproduced, for example, in accordance with U.S. Pat. No. 3,234,258 orU.S. Pat. No. 5,075,041 and which are commercially obtainable asproducts of the Shell Oil Company under the name of DAN®.

The sulfuric acid monoesters of linear or branched C₇₋₂₁ alcoholsethoxylated with 1 to 6 moles of ethylene oxide, such as2-methyl-branched C₉₋₁₁ alcohols containing on average 3.5 moles ofethylene oxide (EO) or C₁₂₋₁₈ fatty alcohols containing 1 to 4 EO, arealso suitable. In view of their high foaming capacity, they are onlyused in relatively small quantities, for example in quantities of 1 to5% by weight, in laundry detergents.

Other preferred anionic surfactants are the salts of alkyl sulfosuccinicacid which are also known as sulfosuccinates or as sulfosuccinic acidesters and which represent monoesters and/or diesters of sulfosuccinicacid with alcohols, preferably fatty alcohols and, more particularly,ethoxylated fatty alcohols. Preferred sulfosuccinates contain C₈₋₁₈fatty alcohol molecules or mixtures thereof. Particularly preferredsulfosuccinates contain a fatty alcohol molecule derived fromethoxylated fatty alcohols which, considered in isolation, representnonionic surfactants (for a description, see below). Of thesesulfosuccinates, those of which the fatty alcohol molecules are derivedfrom narrow-range ethoxylated fatty alcohols are particularly preferred.Alk(en)yl succinic acid preferably containing 8 to 18 carbon atoms inthe alk(en)yl chain or salts thereof may also be used.

Other suitable anionic surfactants are fatty acid derivatives of aminoacids, for example of N-methyl taurine (taurides) and/or of N-methylglycine (sarcosides). The sarcosides or rather sarcosinates, above allsarcosinates of higher and optionally mono- or poly-unsaturated fattyacids, such as oleyl sarcosinate, are particularly preferred.

Other suitable anionic surfactants are, in particular, soaps which arepreferably used in quantities of 0.2 to 5% by weight. Suitable soapsare, in particular, saturated fatty acid soaps, such as the salts oflauric acid, myristic acid, palmitic acid, stearic acid, hydrogenatederucic acid and behenic acid, and soap mixtures derived in particularfrom natural fatty acids, for example coconut oil, palm kernel oil ortallow acids. The known alkenylsuccinic acid salts may also be usedtogether with these soaps or as a substitute for soaps.

The anionic surfactants (and soaps) may be present in the form of theirsodium, potassium or ammonium salts and as soluble salts of organicbases, such as mono-, di- or triethanolamine. The anionic surfactantsare preferably present in the form of their sodium or potassium saltsand, more preferably, in the form of their sodium salts.

The anionic surfactants are present in the detergents according to theinvention and used in the process according to the invention inquantities of preferably 1 to 30% by weight and, more preferably, 5 to25% by weight.

Besides anionic surfactants and cationic, zwitterionic and amphotericsurfactants, nonionic surfactants above all are preferred.

Preferred nonionic surfactants are alkoxylated, advantageouslyethoxylated, more particularly primary alcohols preferably containing 8to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide(EO) per mole of alcohol, in which the alcohol group may be linear or,preferably, 2-methyl-branched or may contain linear and methyl-branchedradicals in the form of the mixtures typically present in oxoalcoholgroups. However, alcohol ethoxylates containing linear residues ofalcohols of native origin with 12 to 18 carbon atoms, for examplecoconut oil fatty alcohol, palm oil fatty alcohol, tallow fatty alcoholor oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol areparticularly preferred. Preferred ethoxylated alcohols include, forexample, C₁₂₋₁₄ alcohols containing 3 EO or 4 EO, C₉₋₁₁ alcoholscontaining 7 EO, C₁₃₋₁₅ alcohols containing 3 EO, 5 EO, 7 EO or 8 EO,C₁₂₋₁₈ alcohols containing 3 EO, 5 EO or 7 EO and mixtures thereof, suchas mixtures of C₁₂₋₁₄ alcohol containing 3 EO and C₁₂₋₁₈ alcoholcontaining 7 EO. The degrees of ethoxylation mentioned are statisticalmean values which, for a special product, may be either a whole numberor a broken number. Preferred alcohol ethoxylates have a narrow homologdistribution (narrow range ethoxylates, NRE). In addition to thesenonionic surfactants, fatty alcohols containing more than 12 EO may alsobe used, as described above. Examples of such fatty alcohols are(tallow) fatty alcohols containing 14 EO, 16 EO, 20EO, 25 EO, 30 EO or40 EO.

The nonionic surfactants also include alkyl glycosides with the generalformula RO(G)_(x) where R is a primary, linear or methyl-branched, moreparticularly 2-methyl-branched, aliphatic radical containing 8 to 22 andpreferably 12 to 18 carbon atoms and G is a glycose unit containing 5 or6 carbon atoms, preferably glucose. The degree of oligomerization x,which indicates the distribution of monoglycosides and oligoglycosides,is a number—which as an analytically determined quantity may even be abroken number—of 1 to 10 and preferably a number of 1.2 to 1.4.

Other suitable surfactants are polyhydroxyfatty acid amidescorresponding to formula (I):

in which R¹CO is an aliphatic acyl grouop containing 6 to 22 carbonatoms, R² is hydrogen, an alkyl or hydroxyalkyl group containing 1 to 4carbon atoms and [Z] is a linear or branched polyhydroxyalkyl groupcontaining 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. Thepolyhydroxyfatty acid amides are preferably derived from reducing sugarscontaining 5 or 6 carbon atoms, more particularly from glucose.

The group of polyhydroxyfatty acid amides also includes compoundscorresponding to formula (II):

in which R³ is a linear or branched alkyl or alkenyl group containing 7to 12 carbon atoms, R⁴ is a linear, branched or cyclic alkyl group or anaryl group containing 2 to 8 carbon atoms and R⁵ is a linear, branchedor cyclic alkyl group or an aryl group or a hydroxyalkyl groupcontaining 1 to 8 carbon atoms, C₁₋₄ alkyl or phenyl groups beingpreferred, and [Z] is a linear polyhydroxyalkyl group, of which thealkyl chain is substituted by at least two hydroxyl groups, oralkoxylated, preferably ethoxylated or propoxylated, derivatives of sucha group. Again, [Z] is preferably obtained by reductive amination of asugar, for example glucose, fructose, maltose, lactose, galactose,mannose or xylose. The N-alkoxy or N-aryloxy-substituted compounds maythen be converted into the required polyhydroxyfatty acid amides byreaction with fatty acid methyl esters in the presence of an alkoxide ascatalyst, for example in accordance with the teaching of Internationalpatent application WO-A-95/07331.

Another class of preferred nonionic surfactants which are used either assole nonionic surfactant or in combination with other nonionicsurfactants, particularly together with alkoxylated fatty alcoholsand/or alkyl glycosides, are alkoxylated, preferably ethoxylated orethoxylated and propoxylated, fatty acid alkyl esters preferablycontaining 1 to 4 carbon atoms in the alkyl chain, more particularly thefatty acid methyl esters which are described, for example, in Japanesepatent application JP 58/217598 or which are preferably produced by theprocess described in International patent application WO-A-90/13533.C₁₂₋₁₈ fatty acid methyl esters containing on average 3 to 15 EO and,more particularly, 5 to 12 EO are preferred as nonionic surfactantswhereas fatty acid methyl esters with a relatively high degree ofethoxylation above all are advantageous as binders, as described above.C₁₂₋₁₈ fatty acid methyl esters containing 10 to 12 EO may be used bothas surfactants and as binders.

Nonionic surfactants of the amine oxide type, for exampleN-coconutalkyl-N,N-dimethylamine oxide andN-tallowalkyl-N,N-dihydroxy-ethyl amine oxide, and the fatty acidalkanolamide type are also suitable. The quantity in which thesenonionic surfactants are used is preferably no more, in particular nomore than half, the quantity of ethoxylated fatty alcohols used.

Other suitable surfactants are so-called gemini surfactants. Geminisurfactants are generally understood to be compounds which contain twohydrophilic groups and two hydrophobic groups per molecule. These groupsare generally separated from one another by a so-called “spacer”. Thespacer is generally a carbon chain which should be long enough for thehydrophilic groups to have a sufficient spacing to be able to actindependently of one another. Gemini surfactants are generallydistinguished by an unusually low critical micelle concentration and byan ability to reduce the surface tension of water to a considerableextent. In exceptional cases, however, gemini surfactants are not onlyunderstood to be dimeric surfactants, but also trimeric surfactants.

Suitable gemini surfactants are, for example, the sulfated hydroxy mixedethers according to German patent application DE-A-43 21 022 and thedimer alcohol bis- and trimer alcohol tris-sulfates and -ether sulfatesaccording to German patent application DE 195 03 061. The end-cappeddimeric and trimeric mixed ethers according to German patent applicationDE 195 13 391 are distinguished in particular by their bifunctionalityand multifunctionality. Thus, the end-capped surfactants mentionedexhibit good wetting properties and are low-foaming so that they areparticularly suitable for use in machine washing or dishwashingprocesses.

However, the gemini polyhydroxyfatty amides or poly-polyhydroxy-fattyacid amides described in International patent applicationsWO-A-95/19953, WO-A-95/19954 and WO-A-95/19955 may also be used.

Apart from surfactants, inorganic and organic builders above all areamong the most important ingredients of detergents.

The finely crystalline, synthetic zeolite containing bound water used inaccordance with the invention is preferably zeolite A and/or zeolite P.Zeolite MAP® (Crosfield), for example, is used as zeolite P. However,zeolite X and mixtures of A, X and/or P are also suitable. The zeolitemay be used in the form of a spray-dried powder or even in the form ofan undried stabilized suspension still moist from its production. Wherethe zeolite is used in the form of a suspension, the suspension maycontain small additions of nonionic surfactants as stabilizers, forexample 1 to 3% by weight, based on zeolite, of ethoxylated C₁₂₋₁₈ fattyalcohols containing 2 to 5 ethylene oxide groups, C₁₂₋₁₄ fatty alcoholscontaining 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.Suitable zeolites have a mean particle size of less than 10 μm (volumedistribution, as measured by the Coulter Counter Method) and containpreferably 18 to 22% by weight and more preferably 20 to 22% by weightof bound water.

Suitable substitutes or partial substitutes for phosphates and zeolitesare crystalline layer-form sodium silicates corresponding to the generalformula NaMSi_(x)O_(2x+1).yH₂O, where M is sodium or hydrogen, x is anumber of 1.9 to 4 and y is a number of 0 to 20, preferred values for xbeing 2, 3 or 4. Crystalline layer silicates such as these aredescribed, for example, in European patent application EP-A-0 164 514.Preferred crystalline layer silicates corresponding to the above formulaare those in which M is sodium and x assumes the value 2 or 3. Both β-and δ-sodium disilicates—Na₂Si₂O₅.yH₂O are particularly preferred.

Other preferred builders are amorphous sodium silicates with a modulus(Na₂O:SiO₂ ratio) of 1:2 to 1:3.3, preferably 1:2 to 1:2.8 and morepreferably 1:2 to 1:2.6 which dissolve with delay and exhibit multiplewash cycle properties. The delay in dissolution in relation toconventional amorphous sodium silicates can have been obtained invarious ways, for example by surface treatment, compounding, compactingor by overdrying. In the context of the invention, the term “amorphous”is also understood to encompass “X-ray amorphous”. In other words, thesilicates do not produce any of the sharp X-ray reflexes typical ofcrystalline substances in X-ray diffraction experiments, but at best oneor more maxima of the scattered X-radiation which have a width ofseveral degrees of the diffraction angle. Particularly good builderproperties may even be achieved where the silicate particles producecrooked or even sharp diffraction maxima in electron diffractionexperiments. This may be interpreted to mean that the products havemicrocrystalline regions between 10 and a few hundred nm in size, valuesof up to at most 50 nm and, more particularly, up to at most 20 nm beingpreferred. So-called X-ray amorphous silicates such as these, which alsodissolve with delay in relation to conventional waterglasses, aredescribed for example in German patent application DE-A-44 00 024.Compacted amorphous silicates, compounded amorphous silicates andoverdried X-ray-amorphous silicates are particularly preferred.

The generally known phosphates may of course also be used as buildersproviding their use is not ecologically problematical. The sodium saltsof orthophosphates, pyrophosphates and, in particular,tripoly-phosphates are particularly suitable. Their content is generallyno more than 25% by weight and preferably no more than 20% by weight,based on the final detergent. In some cases, it has been found thattri-polyphosphates in particular, even in small quantities of up to atmost 10% by weight, based on the final detergent, produce a synergisticimprovement in multiple wash cycle performance in combination with otherbuilders.

Suitable substitutes or partial substitutes for the zeolite are layersilicates of natural and synthetic origin. Such layer silicates areknown, for example, from patent application DE-B-23 34 899, EP-A- 0 026529 and DE-A-35 26 405. Their suitability is not confined to aparticular composition or structural formula. However, smectites,especially bentonites, are preferred.

Suitable layer silicates which belong to the group of water-swellablesmectites are, for example, montmorillonite, hectorite or saponite. Inaddition, small quantities of iron may be incorporated in the crystallattice of the layer silicates in accordance with the above formulae. Byvirtue of their ion-exchanging properties, the layer silicates mayadditionally contain hydrogen, alkali metal, alkaline earth metal ions,more particularly Na⁺ and Ca⁺⁺. The water of hydration content isgenerally between 8 and 20% by weight, depending on the degree ofswelling and the processing technique. Useful layer silicates are known,for example, from U.S. Pat. No. 3,966,629, EP-A-0 026 529 and EP-A-0 028432. Layer silicates substantially freed from calcium ions and stronglycoloring iron ions by an alkali treatment are preferably used.

Useful organic builders are, for example, polycarboxylic acids usable inthe form of their sodium salts, such as citric acid, adipic acid,succinic acid, glutaric acid, tartaric acid, sugar acids,aminocarboxylic acids, nitrilotriacetic acid (NTA), providing their useis not ecologically unsafe, and mixtures thereof. Preferred salts arethe salts of the polycarboxylic acids, such as citric acid, adipic acid,succinic acid, glutaric acid, tartaric acid, sugar acids and mixturesthereof.

The acids per se may also be used. Besides their builder effect, theacids also typically have the property of an acidifying component and,hence, also serve to establish a relatively low and mild pH value indetergents. Citric acid, succinic acid, glutaric acid, adipic acid,gluconic acid and mixtures thereof are particularly mentioned in thisregard. If they are used in the premix according to the invention andare not subsequently added, these acids are preferably used inwater-free form.

Other suitable organic builders are dextrins, for example oligomers orpolymers of carbohydrates which may be obtained by partial hydrolysis ofstarches. The hydrolysis may be carried out by standard methods, forexample acid- or enzyme-catalyzed methods. The end products arepreferably hydrolysis products with average molecular weights of 400 to500,000. A polysaccharide with a dextrose equivalent (DE) of 0.5 to 40and, more particularly, 2 to 30 is preferred, the DE being an acceptedmeasure of the reducing effect of a polysaccharide by comparison withdextrose which has a DE of 100. Both maltodextrins with a DE of 3 to 20and dry glucose sirups with a DE of 20 to 37 and also so-called yellowdextrins and white dextrins with relatively high molecular weights of2,000 to 30,000 may be used. A preferred dextrin is described in Britishpatent application 94 19 091. The oxidized derivatives of such dextrinsare their reaction products with oxidizing agents which are capable ofoxidizing at least one alcohol function of the saccharide ring to thecarboxylic acid function. Dextrins thus oxidized and processes for theirproduction are known, for example, from European patent applicationsEP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 andfrom International patent applications WO-A-92/18542, WO-A-93/08251,WO-A-94/28030, WO-A-95/07303, WO-A-95/12619 and WO-A-95/20608. A productoxidized at C₆ of the saccharide ring can be particularly advantageous.

Other suitable co-builders are oxydisuccinates and other derivatives ofdisuccinates, preferably ethylenediamine disuccinate. The glyceroldisuccinates and glycerol trisuccinates described, for example, in U.S.Pat. No. 4,524,009 in U.S. Pat. No. 4,639,325, in European patentapplication EP-A-0 150 930 and in Japanese patent application JP93/339896 are also particularly preferred in this connection. Thequantities used in zeolite-containing and/or silicate-containingformulations are from 3 to 15% by weight.

Other useful organic co-builders are, for example, acetylatedhydroxycarboxylic acids and salts thereof which may optionally bepresent in lactone form and which contain at least 4 carbon atoms, atleast one hydroxy group and at most two acid groups. Co-builders such asthese are described, for example, in International patent applicationWO-A-95/20029.

Suitable polymeric polycarboxylates are, for example, the sodium saltsof polyacrylic acid or polymethacrylic acid, for example those with arelative molecular weight of 800 to 150,000 (based on acid). Suitablecopolymeric polycarboxylates are, in particular, those of acrylic acidwith methacrylic acid and of acrylic acid or methacrylic acid withmaleic acid. Acrylic acid/maleic acid copolymers containing 50 to 90% byweight of acrylic acid and 50 to 10% by weight of maleic acid haveproved to be particularly suitable. Their relative molecular weight,based on free acids, is generally in the range from 5,000 to 200,000,preferably in the range from 10,000 to 120,000 and more preferably inthe range from 50,000 to 100,000.

The (co)polymeric polycarboxylates may be present in the detergents inthe usual quantities and are preferably present in quantities of 1 to10% by weight.

Also particularly preferred are biodegradable polymers of more than twodifferent monomer units, for example those which contain salts ofacrylic acid and maleic acid and vinyl alcohol or vinyl alcoholderivatives as monomers in accordance with DE-A-43 00 772 or salts ofacrylic acid and 2-alkylallyl sulfonic acid and sugar derivatives asmonomers in accordance with DE-C-42 21 381.

Other preferred copolymers are those described in German patentapplications DE-A-43 03 320 and DE-A-44 17 734 which preferably containacrolein and acrylic acid/acrylic acid salts or acrolein and vinylacetate as monomers.

Other suitable builders are oxidation products of carboxyl-containingpolyglucosans and/or water-soluble salts thereof which are described,for example, in International patent application WO-A-93/08251 or ofwhich the production is described, for example, in International patentapplication WO-A-93/16110. Oxidized oligosaccharides according to Germanpatent application DE-A-196 00 018 are also suitable.

Other preferred builders are polymeric aminodicarboxilic acids, salts orprecursors thereof. Polyaspartic acids or salts and derivatives thereofwhich, according to German patent application DE-A-195 40 086, have ableach-stabilizing effect in addition to their co-builder properties areparticularly preferred.

Other suitable builders are polyacetals which may be obtained byreaction of dialdehydes with polyol carboxylic acids containing 5 to 7carbon atoms and at least three hydroxyl groups, for example asdescribed in European patent application EP-A-0 280 223. Preferredpolyacetals are obtained from dialdehydes, such as glyoxal,glutaraldehyde, terephthal-aldehyde and mixtures thereof and from polyolcarboxylic acids, such as gluconic acid and/or glucoheptonic acid.

The detergents according to the invention may additionally containcomponents which have a positive effect on the removability of oil andfats from textiles by washing. This effect becomes particularly clearwhen a textile which has already been repeatedly washed with a detergentaccording to the invention containing this oil- and fat-dissolvingcomponent is soiled. Preferred oil- and fat-dissolving componentsinclude, for example, nonionic cellulose ethers, such as methylcellulose and methyl hydroxypropyl cellulose containing 15 to 30% byweight of methoxyl groups and 1 to 15% by weight of hydroxypropoxylgroups, based on the nonionic cellulose ether, and the polymers ofphthalic acid and/or terephthalic acid known from the prior art orderivatives thereof, more particularly polymers of ethyleneterephthalates and/or polyethylene glycol terephthalates or anionicallyand/or nonionically modified derlvatives thereof. Of these, thesulfonated derivatives of phthalic and terephthalic acid polymers areparticularly preferred.

Other suitable ingredients of the detergents are water-soluble inorganicsalts, such as bicarbonates, carbonates, amorphous silicates, such asthe above-mentioned silicates dissolving with delay, or mixturesthereof; alkali metal carbonate and amorphous alkali metal silicate,above all sodium silicate with a molar Na₂O:SiO₂ ratio of 1:1 to 1:4.5and preferably 1:2 to 1:3.5, are particularly suitable. The sodiumcarbonate content of the detergents is preferably up to 20% by weightand advantageously between 5 and 15% by weight. If it is not to be usedas a builder, the sodium silicate content of the detergents is generallyup to 10% by weight and preferably between 2 and 8% by weight, otherwisehigher.

The other detergent ingredients include redeposition inhibitors (soilsuspending agents), foam inhibitors, bleaching agents and bleachactivators, optical brighteners, enzymes, fabric softeners, dyes andperfumes and neutral salts, such as sulfates and chlorides in the formof their sodium or potassium salts.

Acidic salts or slightly alkaline salts may also be used to reduce thepH value of detergents. Preferred acidifying components are bisulfatesand/or bicarbonates or the above-mentioned organic polycarboxylic acidswhich may also be used as builders. It is particularly preferred to usecitric acid which is either subsequently incorporated (standardprocedure) or used—in water-free form—in the solid premix.

Among the compounds yielding H₂O₂ in water which serve as bleachingagents, sodium perborate tetrahydrate and sodium perborate monohydrateare particularly important. Other useful bleaching agents are, forexample, sodium percarbonate, peroxypyrophosphates, citrate perhydratesand H₂O₂-yielding peracidic salts or peracids, such as perbenzoates,peroxophthalates, diperazelaic acid, phthaloiminoperacid ordiperdodecanedioic acid. The content of bleaching agents in thedetergents is preferably 5 to 25% by weight and more preferably from 10to 20% by weight, perborate monohydrate or percarbonate advantageouslybeing used.

Suitable bleach activators are compounds which form aliphaticperoxocarboxylic acids containing preferably 1 to 10 carbon atoms andmore preferably 2 to 4 carbon atoms and/or optionally substitutedperbenzoic acid under perhydrolysis conditions. Substances bearingO-and/or N-acyl groups with the number of carbon atoms mentioned and/oroptionally substituted benzoyl groups are suitable. Preferred bleachactivators are polyacylated alkylenediamines, more particularlytetraacetyl ethylenediamine (TAED), acylated triazine derivatives, moreparticularly 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT),acylated glycol-urils, more particularly tetraacetyl glycoluril (TAGU),N-acylimides, more particularly N-nonanoyl succinimide (NOSI), acylatedphenol sulfonates, more particularly n-nonanoyl- orisononanoyl-oxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides,more particularly phthalic anhydride, acylated polyhydric alcohols, moreparticularly triacetin, ethylene glycol diacetate,2,5-diacetoxy-2,5-dihydrofuran and the enol esters known from Germanpatent applications DE-A-196 16 693 and DE-A-196 16 767, acetylatedsorbitol and mannitol and the mixtures thereof (SORMAN) described inEuropean patent application EP-A-0 525 239, acylated sugar derivatives,more particularly pentaacetyl glucose (PAG), pentaacetyl fructose,tetraacetyl xylose and octaacetyl lactose, and acetylated, optionallyN-alkylated glucamine and gluconolactone, and/or N-acylated lactams, forexample N-benzoyl caprolactam, which are known from International patentapplications WO-A-94/27970, WO-A-94/28102, WO-A-94/28103, WO-A-95/00626,WO-A-95/14759 and WO-A-95/17498. The substituted hydrophilic acylacetals known from German patent application DE-A-196 16 769 and theacyl lactams described in German patent application DE-A-196 16 770 andin International patent application WO-A-95/14075 are also preferablyused. The combinations of conventional bleach activators known fromGerman patent application DE-A-44 43 177 may also be used. Bleachactivators such as these are present in the usual quantities, preferablyin quantities of 1% by weight to 10% by weight and more preferably inquantities of 2% by weight to 8% by weight, based on the detergent as awhole.

Where the detergents are used in washing machines, it can be ofadvantage to add typical foam inhibitors to them. Suitable foaminhibitors are, for example, soaps of natural or synthetic origin whichhave a high percentage content of C₁₈₋₂₄ fatty acids. Suitablenon-surface-active foam inhibitors are, for example, organopolysiloxanesand mixtures thereof with microfine, optionally silanized, silica andalso paraffins, waxes, microcrystalline waxes and mixtures thereof withsilanized silica or bis-stearyl ethylenediamide. Mixtures of differentfoam inhibitors, for example mixtures of silicones, paraffins and waxes,may also be used with advantage. The foam inhibitors, more particularlysilicone- and/or paraffin-containing foam inhibitors, are preferablyfixed to a granular water-soluble or water-dispersible support. Mixturesof paraffins and bis-stearyl ethylenediamides are particularlypreferred.

The neutrally reacting sodium salts of, for example,1-hydroxyethane-1,1-diphosphonate, diethylenetriamine pentamethylenephosphonate or ethylenediamine tetramethylene phosphonate in quantitiesof 0.1 to 1.5% by weight are preferably used as the salts ofpolyphosphonic acids.

Suitable enzymes are, in particular, enzymes from the class ofhydrolases, such as proteases, lipases or lipolytic enzymes, amylases,cellulases and mixtures thereof. Oxireductases are also suitable.

Enzymes obtained from bacterial strains or fungi, such as Bacillussubtilis, Bacillus licheniformis, Streptomyces griseus and Humicolainsolens are particularly suitable. Proteases of the subtilisin type arepreferably used, proteases obtained from Bacillus lentus beingparticularly preferred. Of particular interest in this regard are enzymemixtures, for example of protease and amylase or protease and lipase orlipolytic enzymes or protease and cellulase or of cellulase and lipaseor lipolytic enzymes or of protease, amylase and lipase or lipolyticenzymes or protease, lipase or lipolytic enzymes and cellulase, butespecially protease- and/or lipase-containing mixtures or mixtures withlipolytic enzymes. Examples of such lipolytic enzymes are the knowncutinases. Peroxidases or oxidases have also proved to be suitable insome cases. Suitable amylases include in particular α-amylases,isoamylases, pullulanases and pectinases. Preferred cellulases arecellobiohydrolases, endoglucanases and β-glucosidases, which are alsoknown as cellobiases, and mixtures thereof. Since the various cellulasetypes differ in their CMCase and avicelase activities, the desiredactivities can be established by mixing the cellulases in theappropriate ratios.

The enzymes may be adsorbed to supports and/or encapsulated inshell-forming substances to protect them against prematuredecomposition. The percentage content of enzymes, enzyme mixtures orenzyme granules is preferably from about 0.1 to 5% by weight and morepreferably from 0.1 to about 2% by weight.

In addition to phosphonates, the detergents may contain other enzymestabilizers. For example, 0.5 to 1% by weight of sodium formate may beused. Proteases stabilized with soluble calcium salts and having acalcium content of preferably about 1.2% by weight, based on the enzyme,may also be used. Apart from calcium salts, magnesium salts also serveas stabilizers. However, it is of particular advantage to use boroncompounds, for example boric acid, boron oxide, borax and other alkalimetal borates, such as the salts of orthoboric acid (H₃BO₃), metaboricacid (HBO₂) and pyroboric acid (tetraboric acid H₂B₄O₇).

The function of redeposition inhibitors is to keep the soil detachedfrom the fibers suspended in the wash liquor and thus to prevent thesoil from being re-absorbed by the washing. Suitable redepositioninhibitors are water-soluble, generally organic colloids, for examplethe water-soluble salts of polymeric carboxylic acids, glue, gelatine,salts of ether carboxylic acids or ether sulfonic acids of starch orcellulose or salts of acidic sulfuric acid esters of cellulose orstarch. Water-soluble polyamides containing acidic groups are alsosuitable for this purpose. Soluble starch preparations and other starchproducts than those mentioned above, for example degraded starch,aldehyde starches, etc., may also be used. Polyvinyl pyrrolidone is alsosuitable. However, cellulose ethers, such as carboxymethyl cellulose(sodium salt), methyl cellulose, hydroxyalkyl cellulose, and mixedethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropylcellulose, methyl carboxymethyl cellulose and mixtures thereof, andpolyvinyl pyrrolidone are also preferably used, for example inquantities of 0.1 to 5% by weight, based on the detergent.

The detergents may contain derivatives of diaminostilbene disulfonicacid or alkali metal salts thereof as optical brighteners. Suitableoptical brighteners are, for example, salts of4,4′-bis-(2-anilino-4-morpholino-1,3,5-triazinyl-6-amino)-stilbene-2,2′-disulfonicacid or compounds of similar structure which contain a diethanolaminogroup, a methylamino group and anilino group or a 2-methoxyethylaminogroup instead of the morpholino group. Brighteners of the substituteddiphenyl styryl type, for example alkali metal salts of4,4′-bis-(2-sulfostyryl)-diphenyl,4,4′-bis-(4-chloro-3-sulfostyryl)-diphenyl or4-(4-chlorostyryl)-4′-(2-sulfostyryl)-diphenyl, may also be present.Mixtures of the brighteners mentioned may also be used.

EXAMPLES

Granules with the composition shown in Table 1 were produced by spraydrying and, after the addition of other components as listed in Table 2,were processed in a Lödige mixer to form a premix.

TABLE 1 Composition of the spray-dried granules [% by weight] C₉₋₁₃alkyl benzenesulfonate 26.00 Sodium carbonate 8.50 Zeolite 4 A 41.33Optical brightener 0.42 1-Hydroxyethane-1,1-diphosphonic acid 1.00Acrylic acid/maleic acid copolymer, Na salt 9.50 Sodium hydroxide 0.50Salts from solution 0.75 Water 12.00

TABLE 2 Composition of the premix [% by weight] Spray-dried granules(Table 1) 59.0 Sodium perborate monohydrate 20.0 C₁₂₋₁₈ fatty alcohol +7 EO 7.0 C₁₂₋₁₈ fatty alcohol sulfate, 92% 7.5 Polyethylene glycol 40006.0 Perfume oil 0.5

The perfume oil was dissolved in the liquid C₁₂₋₁₈ fatty alcohol +7 EObefore being introduced into the mixer. After leaving the mixer, thefree-flowing premix had a bulk density of 450 g/l and was introducedinto a Lihotz twin-screw extruder in which it was plasticized andextruded under pressure.

The plasticized premix left the extruder under a pressure of 85 barthrough a multiple-bore die (bore diameter 1.4 mm). The extruded strandswere cut by a rotating blade to a length-to-diameter ratio of about 1and were rounded off in a Marumerizer®. After the fine particles (<0.4mm) and coarse particles (>2.0 mm) had been removed by sieving, theextrudate had a bulk density of 810 g/l.

Extrudates E1 and E2 produced in accordance with the invention, whichdiffered in the perfume oils used, were then compared with extrudates C1and C2 of similar composition where the particular perfume oils had beenconventionally sprayed onto the extruded and rounded particles which hadbeen powdered with fine-particle zeolite.

In order to demonstrate the variant according to the invention where theperfumes are divided, another extrudate E3 was produced which containedpart of the perfume and, in addition, was sprayed with the rest of theperfume. This extrudate was compared with an extrudate C3 where all theperfume had been applied by spraying.

The composition of the perfume oils is shown in Table 3. The perfumingof the product and of treated textiles (cotton) was evaluated byperfumists as a subjective odor impression. The figures in theevaluation Table (Table 4) indicate the number of perfumists whichclassified the particular products or the textiles treated with them as“fairly strongly perfuming”. Since a different number of perfumists waspresent in the various perfume tests, the values in the “perfumists”columns do not always add up to the same figure. Accordingly, the firstblock of the first column (product) should be interpreted to mean that 5out 7 perfumists evaluated the extrudates produced in accordance withthe invention as fairly strongly perfuming. The results of the perfumetests are set out in Table 4.

TABLE 3 Composition of the perfume oils [% by weight] Perfume oil 1Bergamot oil 15.0 Dihydromyrcenol 20.0 Citrus oil messina 7.5 Mandarinoil 2.5 Orange oil sweet 5.0 Allyl amyl glycolate 2.0 Cyclovertal 0.5Lavandin oil grosso 2.5 Clary oil 1.0 Lilial 2.0 β-Damascone 0.1Geranium oil bourbon 3.0 Hedione 5.0 Cyclohexyl salicylate 4.0 VertofixCoeur 10.0 Iso-E-super 5.0 Ambroxan 1.6 Ethylene brassylate 10.0 Evernyl1.0 Dipropylene glycol (DPG) 2.3 Perfume oil 2 Phenyl ethyl alcohol 52.0Dimethyl benzyl carbinyl acetate 2.5 Iraldein gamma 5.0 Phenyl aceticacid 0.5 Geranyl acetate 2.0 Benzyl acetate 30.0 Rose oxide L 10% in DPG2.5 Romilate 20.0 Irotyl 0.5 Cyclohexyl salicylate 20.0 Floramate 10.0

TABLE 4 Perfume enhancement (intensity preference) Perfumists (intensitypreference) Damp Dry Product laundry laundry E1 (0.5% perfume oil 1 inextrudate) 5 5 4 C1 (0.5% perfume oil 1 sprayed on) 2 2 3 E2 (0.5%perfume oil 2 in extrudate) 4 5 4 C2 (0.5% perfume oil 2 sprayed on) 2 12 E3 (0.3% perfume oil 2 in extrudate, 5 6 5 0.2% sprayed on) C3 (0.5%perfume oil 2 sprayed on) 1 2 0

What is claimed is:
 1. A process for the production of perfume-enhanceddetergents or detergent components with bulk densities above 600 g/l,comprising a) preparing a solid, substantially water-free premix,containing at least 0.1% by weight of perfume, based on the premix,comprising at least one member selected from the group consisting ofdetergent compounds and detergent raw materials and b) pressagglomerating the premix.
 2. The process as claimed in claim 1 whereinthe premix has a total water content of not more than 15% by weight, thewater not being present in a free form and wherein the content of waternot bound to at least one of zeolite and silicates being not more than10% by weight.
 3. The process as claimed in claim 1 wherein the premixcontains materials which are present as solids at room temperature and 1bar pressure and which have a melting point or softening point no lowerthan 45° C. and, optionally, up to 10% by weight based on the premix ofnonionic surfactants liquid at temperatures below 45° C. and 1 barpressure.
 4. The process as claimed in claim 1 wherein in addition tothe solid constituents, the premix contains up to 10% by weight, ofnonionic surfactants liquid at temperatures below 45° C. and 1 barpressure, the liquid nonionic surfactants being added in the form of amixture with the perfume.
 5. The process as claimed in claim 1 whereinthe premix contains at least one material which is present in solid format temperatures below 45° C. and 1 bar pressure, but which exists as amelt during the press agglomeration step, the melt acting as apolyfunctional water-soluble binder which, in the production of thedetergents, acts both as a lubricant and as an adhesive for the soliddetergent materials, but as a disintegrator during the redissolution ofthe detergent in water.
 6. The process as claimed in claim 1 wherein thepremix contains one or more binders which dissolve almost completely in90 seconds in a concentration of 8 g binder to 1 liter water at 30° C.7. The process as claimed in 1 wherein the premix contains binders whichexist completely as a melt at temperatures of 130° C.
 8. The process asclaimed in claim 1 wherein the binder is introduced into the premix asthe last component, under such conditions that the binder is uniformlydistributed in the mixture of solids as a solidified melt or as apowder.
 9. The process as claimed in claim 1 wherein the binder isincorporated into the premix at a temperature at which the binder existsas a melt.
 10. The process as claimed in claim 1 wherein mixing iscontinued until the melt has solidified and the premix comprises asolid, free-flowing material.
 11. The process as claimed in 1 whereinthe premix comprises a binder content of at least 1% by weight to lessthan 10% by weight based on the premix.
 12. The process as claimed inclaim 1 wherein immediately after leaving a production unit, the pressagglomerated material has temperatures no higher than 90° C.
 13. Theprocess as claimed in claim 1 wherein the premix contains more than0.15% by weight of perfume.
 14. The process as claimed in claim 1wherein at least a portion of the solids forming the premix isintroduced into a mixer and/or granulator at room temperature and theperfume is introduced to the moving bed of solids.
 15. The process asclaimed in claim 1 wherein the perfume is added to the solids togetherwith a binder.
 16. The process as claimed in claim 1 wherein the pressagglomeration step is carried out by at least one method selected fromthe group consisting of extrusion, roller compacting, pelleting andtabletting.
 17. The process as claimed in claim 16, wherein the tools ofthe press agglomerator are at a temperature of at most 150° C. and theprocess temperature is at most 30° C. above the melt temperature or theupper temperature limit to the melting range of the binder.
 18. Theprocess as claimed in claim 16 wherein the heat exposure time in thecompression zone of the press agglomerators is at most 2 minutes. 19.The process as claimed in claim 1 wherein press agglomerating is carriedout by extrusion, wherein the premix is compacted under pressure,plasticized, extruded in strand form through a multiple-bore die in anextruder head and, finally, is size-reduced by a rotating blade, to formsubstantially spherical or cylindrical granules, the temperature in thetransition section of the extruder screw, the predistributor and theextrusion die being controlled in such a way that the meltingtemperature of the binder or the upper limit to the melting range of thebinder is at least reached.
 20. The process as claimed in claim 1wherein the agglomerating is carried out by roller compacting whereinthe premix is compacted under pressure, plasticized, forced betweenrollers to form a sheet-form compactate and size-reduced to granules bymeans of a cutting and size-reducing unit.
 21. The process as claimed inclaim 1 wherein the agglomerating is carried out by pelleting, whereinthe premix is compacted under pressure, plasticized, forced through aperforated plate in the form of fine strands by means of a rotatingroller, and finally, is size-reduced to granules by means of a choppingunit.
 22. A perfume-enhanced detergent wherein at least 80% by weightconsists of components produced in accordance with the process of claim1.
 23. The perfume-enhanced detergent as claimed in claim 22, comprisingfine-particle ingredients bonded together by melt agglomeration as anouter shell.
 24. The perfume-enhanced detergent as claimed in claim 14,which has been subsequently sprayed with perfume.
 25. Theperfume-enhanced detergent as claimed in claim 24, wherein at least 30%by weight of the total perfume present in the detergent has beenintroduced into the detergent before or during this agglomerated step.26. The perfume-enhanced detergent as claimed in claim 26 wherein theproportion of the perfume introduced during the production processcomprises firmly adhering perfumes.
 27. A perfume-enhanced detergent asclaimed in claim 26 wherein the proportion of perfume introduced intothe detergent by the production process comprises mainly readilyvolatile perfumes.